CN105431130A - Cosmetic or dermatological composition comprising a merocyanine, an organic UVB-screening agent and an additional organic UVA-screening agent - Google Patents

Cosmetic or dermatological composition comprising a merocyanine, an organic UVB-screening agent and an additional organic UVA-screening agent Download PDF

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CN105431130A
CN105431130A CN201480017062.1A CN201480017062A CN105431130A CN 105431130 A CN105431130 A CN 105431130A CN 201480017062 A CN201480017062 A CN 201480017062A CN 105431130 A CN105431130 A CN 105431130A
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group
screening agent
compound
uvb
organic
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CN105431130B (en
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A.鲁多
D.康多
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LOreal SA
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LOreal SA
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Priority claimed from FR1350492A external-priority patent/FR3001139B1/en
Priority claimed from FR1350494A external-priority patent/FR3001141B1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/411Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966Triazines or their condensed derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Abstract

The present invention relates to a cosmetic or dermatological composition comprising, in a physiologically acceptable support: a) at least one oily phase and b) at least one merocyanine compound of formula (1 ) defined hereinbelow and c) at least one organic UVB-screening agent chosen from: v) a liquid lipophilic organic UVB-screening agent vi) a hydrophilic organic UVB-screening agent vii) a triazine UVB-screening agent and viii) mixtures thereof; and d) at least one organic UVA-screening agent other than the said merocyanine compound; when the said UVB-screening agent is liquid and lipophilic, the said composition contains less than 2% by weight of cyclohexasiloxane relative to the total weight of the composition. Another subject of the present invention consists of a non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of the said keratin material, of at least one composition according to the invention as defined above. The invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition as defined previously. The invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.

Description

Comprise cosmetics or the dermatological compositions of merocyanine, organic UVB-screening agent and additional organic UVA-screening agent
The present invention relates to cosmetics or dermatological (dermatological) compositions, in physiologically acceptable carrier, it comprises:
A) at least one oil phase, and
B) the merocyanine compound of formula (1) that defines hereinafter of at least one, and
C) the organic UVB-screening agent of at least one, it is selected from
I) the organic UVB-screening agent of liquid lipophilic
Ii) the organic UVB-screening agent of hydrophilic
Iii) triazine UVB-screening agent and
Iv) their mixture; With
D) the organic UVA-screening agent of at least one except described merocyanine compound;
When described UVB-screening agent is liquid and is lipotropy, described compositions comprises the cyclohexasiloxane being less than 2 % by weight, relative to the total weight of said composition.
Another theme of the present invention is by for nurse and/or the non-therapeutic cosmetic method of keratin material of making up is formed, and it comprises surface applied at least one to described keratin material as defined above according to compositions of the present invention.
The invention still further relates to for limiting skin dimmed and/or improve the non-therapeutic cosmetic method of colour of skin color and/or colour of skin uniformity, it comprises surface applied at least one to described keratin material as the compositions defined before.
The invention still further relates to for preventing and/or the non-therapeutic cosmetic method of processing angle protein material aging sign, it comprises surface applied at least one to described keratin material as the compositions defined before.
It is known that wavelength can make the epidermis of people tanned in the radiation of 280nm to 400nm, and wavelength endangers the tanned progress of nature in the radiation (being known as UV-B ray) of 280 to 320nm.Expose the unfavorable change also easily bringing the bio-mechanical property of epidermis, it is reflected in wrinkle and occurs, so that premature skin ageing.
It is also known that wavelength is deeper penetrated in skin than UV-B ray at the UV-A ray of 320 to 400nm.UV-A ray cause skin immediately with lasting blackening (browning).Everyday exposure is in UVA ray under normal operation, can cause the damage of collagen fiber and elastin laminin even at short notice, this be reflected in skin micromorphology change, there is wrinkle and uneven pigmentation (namely brown patch, the colour of skin lack uniformity).
Therefore, the protection for UVA and UVB ray is required.Effective photoprotection product should be protected for UVA and UVB ray simultaneously.
The compositions of multiple photoprotection is proposed so far, to overcome the impact brought out by UVA ray and/or UVB ray.They usually containing with good grounds himself chemical property and according to himself performance by absorbing, the UV-screening agent of organic and/or mineral that works of reflection or scattering UV ray.They comprise and metal oxide pigment usually, fat-soluble organic screening agent of such as titanium dioxide or zinc oxide combination and/or the mixture of water solublity UV-screening agent.
Propose so far for limiting the dimmed multiple cosmetic composition with improving colour of skin color and uniformity of skin.Be well known that in sunscreen product field, such compositions can be passed through to use UV-screening agent, and particularly UVB-screening agent obtains.Some compositions also can contain UVA screening agent.In order to limit and control to promote total Pigmented melanic new synthesis (neosynthesis), this shading system should contain UVB protection, but also should contain UVA protection, to limit and to control the already present melanic oxidation that causes skin color dimmed.
But, be very difficult to find the compositions containing being particularly suitable for improving the specific combination of the UV-screening agent of skin tone with regard to color and its mechanical elasticity performance.Pigmented skin searches out this improvement especially, thus the melanin structure not increasing melanic pigment load (pigmentaryload) or be present in skin.
In fact, most of organic UV-screening agent is made up of the aromatic compounds absorbed in the wave-length coverage of 280 to 370nm.Except the ability of its shielded from sunlight, required photoprotection compound also should have good cosmetic properties, at common solvents when the combination separately or with other UV-screening agent, and particularly at fatty material, such as, good solubility in oil, and good chemical stability and good light stability.They also should be colourless, or at least have cosmetically acceptable color for consumers.
One of hitherto known major defect of these sunscreen compositions is, in order to by the system for covering the UV in whole UV spectrum to control photoinduced pigmentation and development thereof, for UV ray and particularly for wavelength more than the long UVA ray of 370nm they be not enough effective for covering the system of UVA and UVB radiation.
The organic UVB-screening agent of liquid lipophilic has superiority especially, because they do not need solvent they to be dissolved in the oil that is usually used in sunscreen composition.These liquid UV B-screening agent are mainly selected from β, β-diphenylacrylate ester compounds, such as octocrylene (Octocrylene), salicylate compounds, such as homosalate (homosalate) and ethylhexyl salicylate, and cinnamate compound, such as ethylhexyl methoxy cinnamate.
But UVA and the UVB shading system containing these liquid organic UVB-screening agent combined with conventional organic UVA-screening agent does not provide the wide UV within the scope of whole 280-400nm to protect.
The organic UVB-screening agent of hydrophilic has superiority especially, because they can be dissolved in the amount also therefore limiting the oil be usually used in sunscreen composition in aqueous phase.In conventional hydrophilic UVB-screening agent, phenylbenzimidazol compound can be mentioned, the Phenylbenzimidazolesulfonic acid such as sold with the trade name of Eusolex232 by Merck especially.
But UVA and the UVB shading system containing these hydrophilic organic UVB-screening agent combined with conventional organic UVA-screening agent does not provide the wide UV within the scope of whole 280-400nm to protect.
Because their gratifying UVB-ray absorption properties, triazine UVB-screening agent has superiority especially.They are described in patent US4724137, EP0517104, EP0570838, EP0796851 and EP0775698.Product known especially comprises derivant 2,4,6-tri-[p-(2'-ethylhexyl-1'-oxygen base carbonyl) anilino-]-1,3,5-triazine, it is sold with the trade name of UvinulT150 by BASF AG especially, with 2-[(p-(tert-butyl amide groups) anilino-]-4,6-pair [(p-(2 '-ethylhexyl-1 '-oxygen base carbonyl) anilino-]-1,3,5-triazine or Diethylhexyl Butamido Triazon (INCI title), sold with UvasorbHEB trade name by Sigma3V.
But the UVB-combined containing these and conventional organic UVA-screening agent covers UVA and the UVB shading system of triazine not,
Merocyanine compound is at patent US4195999, patent application WO2004/006878, patent application WO2008/090066, WO2011/113718, WO2009/027258, WO2013010590, WO2013/011094, WO2013/011480 and file: the IPCOMJOURNALN ° of 000179675D being published on February 23rd, 2009, be published in the IPCOMJOURNALN ° of 000182396D on April 29, be published in the IPCOMJOURNALN ° of 000189542D on November 12nd, 2009, be published in the IPCOMJournalN ° of IPCOM000011179D of 03/04/2004 known.
Some in these compounds may show following shortcoming:
-at common solvents and especially at fatty material, such as, relatively not satisfied dissolubility in oil, this may need the process for preparation of effort and/or may cause cosmetics shortcoming, such as, greasy effect when using;
-not satisfied chemical stability and/or not satisfied light stability;
-producing color, it is easy to the cosmetics or the dermatological compositions that hinder consumer's use to contain them.
UVA and UVB shading system, it is made up of following: some in (1) these merocyanine screening agent, as corresponded to the compound 5-N of the compound MC172 of following structure, N-diethylamino-2-benzenesulfonyl-2,4-pentadienoic acid monooctyl ester
(2) at least one organic liquid lipotropy UVB filtering agent (filter) and/or a kind of organic hydrophilicity UVB filtering agent and/or a kind of triazine UVB filtering agent and the conventional organic UVA filtering agent of (3) at least one, this UVA and UVB shading system always can not provide the wide UV protection within the scope of 280-400nm, and particularly obtains the observable absorption of as many as 400nm (comprising 400nm) wavelength.
Therefore, still there is the demand to finding novel UVA and UVB shading system, described system is based on (1) at least one merocyanine compound, (2) at least one UVB-screening agent, it is a kind of organic liquid lipotropy UVB filtering agent and/or a kind of organic hydrophilicity UVB filtering agent and/or a kind of triazine type UVB filtering agent and the organic UVA filtering agent of at least one, described system is that light is stable, and to guarantee the full protection to 280-400nmUV ray with the mode of high temperatures in time, there is the remarkable absorption of as many as 400nm (comprising 400nm) wavelength especially, and there is no the shortcoming as defined before.
Applicant finds astoundingly, by using a) at least one organic liquid lipotropy UVB filtering agent and/or at least one organic hydrophilicity UVB filtering agent and/or at least one UVB triazine filtering agent, b) specific formula (1) merocyanine, it is by specific definition and the organic UVA filtering agent of at least one c) except described merocyanine can realize this object hereinafter.
In addition, compared to being disclosed in application WO2008/090066 as compound MC11 with also at the merocyanine compound applying for being called in WO2009/027258 MC03, the merocyanine compound of formula (1) herein presents astoundingly and has remarkable less painted advantage below.
These find to form basis of the present invention.
Therefore according to an object of the present invention, now propose cosmetics or dermatological compositions, in physiologically acceptable carrier, it comprises:
A) at least one oil phase, and
B) the merocyanine compound of formula (1) that defines hereinafter of at least one, and
C) the organic UVB-screening agent of at least one, it is selected from
I) the organic UVB-screening agent of liquid lipophilic
Ii) the organic UVB-screening agent of hydrophilic
Iii) triazine UVB-screening agent and
Iv) their mixture; With
D) the organic UVA-screening agent of at least one except described merocyanine compound;
When described UVB-screening agent is liquid and is lipotropy, described compositions comprises the cyclohexasiloxane being less than 2 % by weight, relative to the total weight of said composition.
Another theme of the present invention is by for nurse and/or the non-therapeutic cosmetic method of keratin material of making up is formed, and it comprises surface applied at least one to described keratin material as defined above according to compositions of the present invention.
The invention still further relates to for limiting skin dimmed and/or improve the non-therapeutic cosmetic method of colour of skin color and/or colour of skin uniformity, it comprises surface applied at least one to described keratin material as the compositions defined before.
The invention still further relates to for preventing and/or the non-therapeutic cosmetic method of processing angle protein material aging sign, it comprises surface applied at least one to described keratin material as the compositions defined before.
Further feature of the present invention, aspect and advantage will manifest reading in following detailed description.
Statement " human keratin material " means skin (health, face, near the eyes region), hair, eyelashes, eyebrow, chaeta, fingernail, lip or mucosa.
Term " physiology can accept " to mean and skin and/or its crust (integument) compatibility mutually, it has desirable color, abnormal smells from the patient and sense of touch, and does not cause and be easy to hinder consumer to use any unacceptable discomfort (sensation of pricking, tight sense or rubescent) of said composition.
Term " liquid lipophilic organic UVB-screening agent " means any organic chemistry molecule of the UVB ray that can absorb at least 280-320nm wave-length coverage; Described molecule is liquid form under room temperature (20-25 DEG C) and under atmospheric pressure (760mmHg), and can with molecular forms be fully dissolved in liquid aliphatic mutually in, or its can in colloidal form (such as with micelle form) be dissolved in liquid aliphatic mutually in.
Term " hydrophilic organic UVB-screening agent " means any organic chemistry molecule of the UVB ray that can absorb at least 280-320nm wave-length coverage; Described molecule fully can be dissolved in aqueous phase with molecular forms, or it can (such as with micelle form) be dissolved in aqueous phase in colloidal form.
Term " organic UVA-screening agent " means any organic chemistry molecule of the UVA ray that can absorb at least 320-400nm wave-length coverage; Described molecule can also absorb the UVB ray in 280-320nm wave-length coverage.
Term " X to Y " means the value scope also comprising ultimate value X and Y.
According to the present invention, term " prevention " (" preventing " or " prevention ") means the phenomenon reducing and occur providing, namely according to the risk of keratin material aging sign of the present invention, or its appearance of slowing down.
merocyanine
According to the present invention, correspond to following formula (1) according to merocyanine compound of the present invention, and itself E/E-or E/Z-geometric isomer form:
Wherein:
R is C 1-C 22alkyl, C 2-C 22thiazolinyl, C 2-C 22alkynyl, C 3-C 22cycloalkyl or C 3-C 22cycloalkenyl group, described group can be replaced by one or more O.
Merocyanine compound of the present invention can be itself E/E-or E/Z-geometric isomer form.
Preferred formula (1) compound is wherein:
R is C 1-C 22alkyl, its can be interrupted by one or more O those.
In formula (1) compound, be selected from those of following compound and itself E/E-or E/Z-geometric isomer form by more particularly using:
The special pattern of one according to the present invention, is selected from those of following compound by use, and itself E/E-or E/Z-geometric isomer form:
According to one of the present invention particularly preferred pattern, compound (2Z)-cyano group { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } 2-ethoxyethyl acetate (2) will be used, in its E/Z geometric configuration, there is following structure:
And/or in its E/E geometric configuration, there is following structure:
According to the merocyanine of formula of the present invention (1) preferably in compositions according to the present invention with 0.1 % by weight to 10 % by weight, and preferably 0.2 % by weight to 5 % by weight concentration exist, relative to the total weight of said composition.
The compound of formula (1) can according to being described in patent application WO2007/071582, in IP.comJournal (2009), 9 (5A), 29-30IPCOM000182396D is entitled as " Processforproducing3-amino-2-cyclohexan-1-ylidenecompoun ds " and US-A-4749643, prepared by the experimental program in the 13rd hurdle the 66th Hang – the 14th hurdle the 57th row and the list of references at this point quoted.
the organic UVB-screening agent of liquid lipophilic
Be preferably selected from according to the organic UVB-screening agent of the operable liquid of the present invention:
-liquid lipophilic β, β-diphenylacrylate ester compounds
-liquid lipophilic salicylate compounds
-liquid lipophilic cinnamate compound
-and their mixture.
a) β, β-diphenylacrylate ester compounds
According in the present invention's operable organic liquid lipotropy UVB-screening agent, the liquid lipophilic β of following formula (I) can be mentioned, β-diphenylacrylate Arrcostab or alpha-cyano-β, β-diphenylacrylate ester compounds:
Wherein R 1to R 3following implication can be had:
-R 1and R' 1, it can be identical or different, represents hydrogen atom, straight chain or side chain C 1-C 8alkoxy base or straight chain or side chain C 1-C 4alkyl group;
-R 1and R' 1in a position or para-position;
-R 2represent straight chain or side chain C 1-C 12alkyl group;
-R 3represent hydrogen atom or CN group.
Straight chain or side chain C 1-C 8in alkoxy base, the example that can mention comprise methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, neopentyl oxygen, positive hexyloxy, positive heptan oxygen base, n-octyloxy and 2-ethyl hexyl oxy group.
Straight chain or side chain C 1-C 4in alkyl group, more particularly can it is mentioned that methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and tertiary butyl groups.C 1-C 12in alkyl group, except above-mentioned except those, the example that can also mention comprises n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, decyl and dodecyl group.
In the compound of general formula (I), particularly preferred following compound:
Alpha-cyano-β, β-diphenylacrylate 2-Octyl Nitrite,
Alpha-cyano-β, β-diphenyl-ethyl acrylate, the etocryene such as sold with the trade name of UvinulN35 by BASF especially (Etocrylene),
β, β-diphenylacrylate 2-Octyl Nitrite,
β, β-bis-(4' methoxyphenyl) ethyl acrylate.
In the compound of general formula (I), even particularly preferred compound Octocrylene or octocrylene (Octocrylene), especially by BASF with the sold of UvinulN539 commodity.
b) salicylate compounds:
According in the operable liquid lipophilic salicylate compounds of the present invention, can it is mentioned that:
-homosalate, its by Rona/EMIndustries with EusolexHMS sold,
-ethylhexyl salicylate, its by Symrise with NeoHeliopanOS sold.
c) cinnamate compound:
According in the operable liquid lipophilic cinnamate compound of the present invention, can it is mentioned that:
-ethylhexyl methoxy cinnamate, it is sold with the trade name of ParsolMCX by DSMNutritionalProducts especially,
-methoxycinnamate isopropyl propionate,
-methoxycinnamate isoamyl valerate, it is sold with the trade name of NeoHeliopanE1000 by Symrise.
According in liquid lipophilic UVB-screening agent of the present invention, the compound particularly used is selected from:
-octocrylene,
-homosalate,
-ethylhexyl salicylate,
-ethylhexyl methoxy cinnamate, and their mixture.
In these liquid lipophilic UVB-screening agent, the compound more preferably used is selected from:
-octocrylene,
-ethylhexyl salicylate, and their mixture, and be even more particularly octocrylene.
According to liquid lipophilic UVB-screening agent (one or more) of the present invention preferably in compositions according to the present invention with 0.1 % by weight to 40 % by weight, preferably 0.2 % by weight to 25 % by weight, and even more preferably the concentration of 0.5 % by weight to 15 % by weight exists, relative to the total weight of said composition.
the organic UVB-screening agent of hydrophilic
The organic UVB-screening agent of hydrophilic is selected from especially:
-hydrophilic cinnamon derivative, such as ferulic acid or ferulic acid;
-hydrophilic benzylidene camphor compound;
-hydrophilic phenylbenzimidazol compound;
-hydrophilic Para-Aminobenzoic (PABA) compound;
-hydrophilic salicylic acid compound;
-and their mixture.
As the example of the organic UVB-screening agent of hydrophilic, can it is mentioned that hereafter represent with their INCI title those:
para-Aminobenzoic compound:
PABA,
PEG-25PABA, its by BASF with the sold of UvinulP25.
salicylic acid compound:
Dipropylene glycol salicylate, its by Scher with the sold of Dipsal,
TEA salicylate, its by Symrise with the sold of NeoHeliopanTS.
benzylidene camphor compound:
Benzylidene camphor sulfonic acid, its by Chimex with the title manufacture of MexorylSL,
Camphora benzene prick ammonium methyl sulphate, its by Chimex with the title manufacture of MexorylSO.
phenylbenzimidazol compound:
Phenylbenzimidazolesulfonic acid, it is sold with the trade name of Eusolex232 by Merck especially.
To particularly use screening agent Phenylbenzimidazolesulfonic acid, it is sold with the trade name of Eusolex232 by Merck especially.
Hydrophilic UVB-screening agent (one or more) can with 0.1 % by weight to 15 % by weight in compositions according to the present invention, and preferably the content of 0.2 % by weight to 10 % by weight exists, relative to the total weight of said composition.
triazine UVB-screening agent
According in triazine UVB-screening agent of the present invention, the 1,3,5-triazines derivant of following formula (I) can be mentioned
Wherein A 1, A 2and A 3group, it can be identical or different, is selected from the group of formula (II):
Wherein:
-X a, it can be identical or different, represents oxygen or-NH-group;
-R a, it can be identical or different, is selected from straight chain or side chain C 1-C 18alkyl group; C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; Polyoxyethylene group, it comprises 1-6 ethylene oxide unit, and wherein terminal OH groups is methylated; The group of following formula (III), (IV) or (V):
Wherein:
-R 1for hydrogen or methyl group;
-R 2for C 1-C 9alkyl group;
-q is the integer of 0-3;
-r is the integer of 1-10;
-A' is C 4-C 8alkyl group or C 5-C 8group of naphthene base;
-B' is selected from: straight chain or side chain C 1-C 8alkyl group; C 5-C 8group of naphthene base; Optionally by one or more C 1-C 4the aromatic yl group that alkyl group replaces.
Understand, A 1, A 2and A 3identical and X awhen representing oxygen atom, then R arepresent side chain C 6-C 18alkyl group.
The same clan of first particularly 1,3,5-triazines derivant of preferred formula (I) is described in the compound in file EP-A-0517104 especially, and it corresponds to the 1,3,5-triazines of formula (I), wherein A 1, A 2and A 3there is formula (II) structure, and there is following characteristics:
-one or two radicals X a-R arepresent group-NH-R a, R abe selected from: C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; The group of above formula (III), (IV) or (V), wherein:
-B' is C 1-C 4alkyl group;
-R 2for methyl group;
-another two X a-R arepresent group-O-R a, R a, it can be identical or different, is selected from: hydrogen; Alkali metal; Ammonium group, it is optionally replaced by one or more alkyl or hydroxyalkyl group; Straight chain or side chain C 1-C 18alkyl group; C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; The group of above formula (III), (IV) or (V), wherein:
-B' is C 1-C 4alkyl group;
-R 2for methyl group;
The same clan of second particularly compound of preferred formula (I) is the compound be made up of 1,3,5-triazines derivant be described in file EP-A-0570838, and it corresponds to the 1,3,5-triazines of formula (I), wherein A 1, A 2and A 3there is formula (II) structure, and there is whole following characteristics:
-one or two radicals X a-R arepresent group-NH-R a, R abe selected from: straight chain or side chain C 1-C 18alkyl group; C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; The group of above formula (III), (IV) or (V), wherein:
-B' is C 1-C 4alkyl group;
-R 2for methyl group;
-another or another two X a-R afor group-O-R a, R a, it can be identical or different, is selected from: hydrogen; Alkali metal; Ammonium group, it is optionally replaced by one or more alkyl or hydroxyalkyl group; Straight chain or side chain C 1-C 18alkyl group; C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; The group of above formula (III), (IV) or (V), wherein:
-B' is C 1-C 4alkyl group;
-R 2for methyl group;
The same clan of the compound of the formula (I) in the 3rd preferred situation used in the present invention, and it is described in file US4724137 especially, and it corresponds to the 1,3,5-triazines of formula (I), wherein A 1, A 2and A 3there is formula (II) structure, and there is following characteristics:
-X abe identical and represent oxygen;
-R a, it can be identical or different, represents C 6-C 12alkyl group or polyalkylene oxide groups, it comprises 1-6 ethylene oxide unit, and wherein terminal OH groups is methylated.
In the triazine UVB compound of formula (I), below particularly selecting:
-2-[(p-(tert-butyl amide groups) anilino-]-4,6-pair [(p-(2 '-ethylhexyl-1 '-oxygen base carbonyl) anilino-]-1,3,5-triazine or Diethylhexyl Butamido Triazon, it is sold with the trade name of UvasorbHEB by Sigma3V, and corresponds to following formula:
Wherein R''' represents 2-ethylhexyl group, and R'' represents tert-butyl group;
-2,4,6-tri-[p-(2'-ethylhexyl-1'-oxygen base carbonyl) anilino-]-1,3,5-triazines or Uvinul T 150, it is sold with the trade name of UvinulT150 by BASF AG especially, and corresponds to following formula:
Wherein R''' represents 2-ethylhexyl group,
-and their mixture.
According in triazine UVB-screening agent of the present invention, the silicone triazine (siliconetriazine) of following formula (VI) can also be mentioned, or its tautomeric form:
Wherein:
-R, it can be identical or different, represents straight chain or side chain C 1-C 30hydrocarbyl group, it is optionally halogenated or undersaturated, C 6-C 12aromatic yl group, C 1-C 10alkoxy base, oh group or trimethylsiloxy group;
-group (D) represents the sym-triazine compound of following formula (VII):
Wherein:
-X represents-O-or-NR 10-, R 10represent hydrogen or C 1-C 5alkyl group,
-R 8represent optionally undersaturated straight chain or side chain C 1-C 30hydrocarbyl group, and it can comprise silicon atom, C 5-C 20group of naphthene base, it is optionally by 1-3 straight chain or side chain C 1-C 4alkyl group replaces, group-(CH 2cHR 10-O) mr 11or group-CH 2-CH (OH)-CH 2-O-R 12,
-R 9, it can be identical or different, represents oh group, straight chain or side chain C 1-C 8alkyl group or C 1-C 8alkoxy base, the R of two vicinities on identical aromatic ring 2group may form alkylenedioxy group (alkylidenedioxy) group together, and wherein alkylidene group contains 1 or 2 carbon atoms,
-R 10represent hydrogen or methyl; Group (C=O) XR 8relative to amino may at ortho position, a position or para-position,
-R 11represent hydrogen or C 1-C 8alkyl,
-R 12represent hydrogen or C 4-C 8alkyl,
-m is the integer of 2-20,
-n=0 to 2,
-A is for being selected from methylene or corresponding to the divalent group of following formula (VIII), (IX), group one of in (X) or (XI):
Wherein:
-Z is the C of saturated or unsaturated, straight chain or side chain 1-C 10alkylidene divalent group (diradical), it is optionally replaced by oh group or oxygen atom and optionally comprises amino;
-W represents hydrogen atom, oh group or straight chain or side chain, saturated or undersaturated C 1-C 8hydrocarbyl group.
The organosiloxane of formula (VI) can be contained: (R) b-(Si) (O) (4-b)/2unit, wherein R has the implication identical with formula (VI), b=1,2 or 3.
It should be noted that the derivant of formula (VI) with their tautomeric form, and more especially can use with the tautomeric form of following formula (VI'):
Wherein group (D') represents the sym-triazine compound of following formula (VII'):
Except formula-A-(Si) (Ra) (O) (3-a)/2unit outside, organosiloxane can also contained (R 1) b-(Si) (O) (4-b)/2unit, wherein R 1there is the implication identical with formula (VI), b=1,2 or 3.
In formula as defined above (VI) and (VI'), hydrocarbyl group can be straight chain or side chain, saturated or undersaturated, and be selected from methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tertiary octyl groups especially.Particularly preferred hydrocarbyl group is methyl group.
Preferred sym-triazine derivant is wherein in formula (VI) or (VI'), meets at least one and those of even more preferably whole following characteristics:
R is methyl,
A=1 or 2,
R 8for C 2-C 8group,
Z=-CH 2-,
W=H。
Preferably, the sym-triazine compound of formula of the present invention (VI) is represented by following formula (VIa), (VIb) or (VIc):
(VIc)(D)-Si(R 14) 3
Wherein:
-(D) corresponding to formula as defined above (VII),
-R 13, it can be identical or different, is selected from straight chain or side chain C 1-C 20alkyl, phenyl, 3,3,3-trifluoro propyls and trimethylsiloxy group or oh group,
-R 14, it can be identical or different, is selected from straight chain or side chain C 1-C 20alkyl and alkenyl group, oh group or phenyl group,
-(B), it can be identical or different, is selected from R 13group and (D) group,
-r is the integer of 0-200 (comprising end points),
-s is the integer of 0-50, and if s=0, then and at least one expression (D) of two (B) symbols,
-u is the integer of 1-10,
-t is the integer of 0-10, understanding be that t+u is equal to, or greater than 3, and their tautomeric form.
Straight chain two organosiloxane of formula (VIa)
Straight chain or ring-type two organosiloxane of formula (VIa) or (VIb) are random oligomer or polymer, and it preferably has at least one and even more preferably whole following characteristics:
-R 13for methyl group, C 1-C 2alkoxy base or oh group,
-B preferable methyl (when the straight chain compound of formula (VIa))
As the example of the particularly preferably compound of formula (VI), following formula (VI will be mentioned 1)-(VI 14) compound and their tautomeric form:
r=8.1。
To particularly use structure (VI 2) compound 2, two (the positive butyl ester of 4'-bis-base the amino benzoic Acid)-6-{ [1 of 4-, 3,3,3-tetramethyl-1-[(trimethyl silyl) oxygen base] disiloxane base] propyl group-3-base amino }-sym-triazine (2,4-bis (n-butyl4'-diylaminobenzoate)-6-{ [1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] disiloxanyl] propyl-3-ylamino}-s-triazine):
Triazine and the synthesis thereof of formula (VI) are described in patent application EP1891079.
According in the operable triazine UVB-screening agent of the present invention, the sym-triazine with toluenyl malonic ester and/or cinnamate and/or benzylidene camphor and/or benzotriazole functional group replacement can also be mentioned, such as:
2,4,6-tri-(the amino benzal malonic acid diisobutyl ester of 4'-)-sym-triazine,
2,4,6-tri-(amino benzal malonic acid-bis-(2-ethylhexyl) ester of 4'-)-sym-triazine,
2,4,6-tri-(amino benzal malonic acid-bis-(2-ethylhexyl) ester of 4'-) the chloro-sym-triazine of-6-,
2,4,6-tri-(amino benzal malonic acid-bis-(2-ethylhexyl) ester of 4'-)-6-(4'-amino benzoic Acid 2-Octyl Nitrite)-sym-triazine,
2,4,6-tri-(the amino benzal malonic acid diisobutyl ester of 4'-)-6-butoxy-sym-triazine,
2,4,6-tri-(the amino benzal malonic acid diisobutyl ester of 4'-)-6-(2-ethylhexylamino)-sym-triazine,
2,4-two (the amino benzylidene camphor of 4'-)-6-(2-ethylhexylamino)-sym-triazine,
2,4-two (the amino benzylidene camphor of 4'-)-6-(the amino benzal malonic acid diisobutyl ester of 4'-)-sym-triazine,
-2,4,6-tri-(the amino benzal malonic acid diethylester of 4'-)-sym-triazine,
-2,4,6-tri-(the amino benzal malonic acid diisopropyl ester of 4'-)-sym-triazine,
-2,4,6-tri-(the amino benzal malonic acid dimethyl ester of 4'-)-sym-triazine,
-2,4,6-tri-(alpha-cyano-4-amino cinnamate)-sym-triazine,
-2,4,6-tri-[(3'-benzotriazole-2-base-2'-hydroxyl-5'-methyl) phenyl amino]-sym-triazine,
-2,4,6-tri-[(3'-benzotriazole-2-base-2'-hydroxyl-5'-uncle-octyl group) phenyl amino]-sym-triazine.
Triazine UVB-screening agent according to the present invention is preferred with 0.1 % by weight to 30 % by weight in compositions according to the present invention, preferably 0.2 % by weight to 20 % by weight, and even more preferably the concentration of 0.5 % by weight to 10 % by weight exists, relative to the total weight of said composition.
organic UVA-screening agent
Compositions according to the present invention comprises the organic UVA-screening agent of at least one.They are selected from hydrophilic, lipotropy or insoluble organic UVA-screening agent usually.
Term " hydrophilic UV-screening agent " means the compound of the organic or mineral for any cosmetics or dermatological covering UV radiation, it fully can be dissolved in liquid aqueous phase with molecular forms, or it can (such as with micelle form) be dissolved in liquid aqueous phase in colloidal form.
Term " lipotropy screening agent " means the compound of the organic or mineral for any cosmetics or dermatological covering UV radiation, its can with molecular forms be fully dissolved in liquid aliphatic mutually in, or its can in colloidal form (such as with micelle form) be dissolved in liquid aliphatic mutually in.
Term " insoluble UV-screening agent " means the compound of the organic or mineral for any cosmetics or dermatological covering UV radiation, it has the dissolubility in water being less than 0.5 % by weight, with the dissolubility in most of organic solvent being less than 0.5 % by weight, this organic solvent is such as liquid paraffin, fatty alcohol benzoates (fattyalkylbenzoate) and fatty acid triglycercide, such as, by the Miglyol812 of DynamitNobel Company.This dissolubility determined at 70 DEG C is defined as with return to room temperature after the amount of product under the solution state in a solvent that balances of Excess solid in suspension.It can easily be evaluated in the lab.
In organic UVA-screening agent of the present invention, can mention:
Organic UVA-screening agent of-type (A), it exclusively can absorb the UV ray of 320-400nm,
Organic UVA-screening agent of-type (B), it can the UV ray of simultaneously stability 280-320nm and 320-400nm,
-and their mixture.
A) organic UVA-screening agent of the type (A) of the UV ray of 320-400nm can be absorbed
Organic UVA-screening agent of type (A) is preferably selected from dibenzoylmethane compounds: the amino hydroxybenzophenone compound replaced, and it is as described in patent application EP-A-1046391, EP1133980, DE10012408 and WO2007/071584; O-amino benzoyl acid compound; Benzylidene camphor compound; 4,4-diaryl adiene cpd, such as, described in patent EP916335 and EP1133981 those; Two-benzoxazolyl group (bis-benzazolyl) compound, as described in patent EP669323 and US246326; With their mixture, and more especially following organic UVA-screening agent:
dibenzoylmethane compounds:
Butyl methoxydibenzoylmethise, it is sold with the trade name of Parsol1789 by DSMNutritionalProductsInc. especially;
Isopropyl dibenzoyl methane.
the amino hydroxybenzophenone compound replaced:
2-(4-diethylamino-2-hydroxy benzoyl) the n-own ester of benzoic acid, it is sold with the trade name of UvinulAPlus by BASF AG.
1,1'-(Isosorbide-5-Nitrae-piperazine two base) two [1-[2-[4-(diethylamino)-2-hydroxy benzoyl]-phenyl]-ketone] (CAS919803-06-8), such as, be described in patent application WO2007/071584; Advantageously use this compound (average-size 0.02 to 2 μm) with micronized form, it such as can obtain according to the micronize technique being described in patent application GB-A-2303549 and EP-A-893119, and particularly with the form of aqueous dispersion.
o-amino benzoyl acid compound:
Antisolaire, it is sold with the trade name of NeoHeliopanMA by Symrise especially.
4,4-diaryl adiene cpd:
1,1-dicarboxyl (2,2'-dimethyl propyl)-4,4-diphenyl diethylenes.
benzylidene camphor compound:
Terephthalidene Dicamphor Sulfonic Acid, its by Chimex with the title manufacture of MexorylSX.
two-benzoxazolyl stilbenes:
Phenyl dibenzimidazole tetrasulfonic acid ester disodium, it is sold with the trade name of NeoHeliopanAP by HaarmannandReimer.
In the present case and according to specific embodiments, use organic screening agent of following type (A):
-butyl methoxydibenzoylmethise;
-2-(4-diethylamino-2-hydroxy benzoyl) the n-own ester of benzoic acid;
-Terephthalidene Dicamphor Sulfonic Acid, and their mixture.
b) organic UVA-screening agent of the mixed type (B) of both UVA and UVB can be absorbed
Organic UVA-screening agent of type (B) is preferably selected from: benzophenone cpd, phenyl benzotriazole cpd, di-2-ethylhexylphosphine oxide (hydroxy phenyl benzotriazole) compound, as described in patent application US5237071, US5166355, GB2303549, DE19726184 and EP893119, two-resorcinol group triaizine compounds, as described in patent application EP0775698, benzoazole compounds, as described in patent application EP0832642, EP1027883, EP1300137 and DE10162844, by the triazine screening agent of the symmetry that naphthyl or polyphenylene replace, it is described in patent US6225467, patent application WO2004/085412(is see compound 6 and 9) or file " SymmetricalTriazineDerivatives ", IP.COMIPCOM000031257Journal, INC, WestHenrietta, NY, US(2004 JIUYUE 20 days) in, particularly 2, 4, 6-tri-(diphenyl) triazine and 2, 4, 6-tri-(terphenyl) triazine, it is at patent application WO06/035000, WO06/034982, WO06/034991, WO06/035007, be discussed in WO2006/034992 and WO2006/034985, advantageously use these compounds with micronised form (particle mean size of 0.02 to 3 μm), it can such as obtain according to the micronize technique be described in patent application GB-A-2303549 and EP-A-893119, and particularly with aqueous dispersion, with their mixture.
benzophenone cpd:
BP-1, it is sold with the trade name of Uvinul400 by BASF especially;
BP-2, it is sold with the trade name of UvinulD50 by BASF especially;
BP-3 or oxybenzone, it is sold with the trade name of UvinulM40 by BASF especially;
UVINUL MS 40, its by BASF AG with the sold of UvinulMS40;
Benzophenone-5;
Benzophenone-6, it is sold with the trade name of Helisorb11 by Norquay especially;
Benzophenone-8, it is sold with the trade name of Spectra-SorbUV-24 by AmericanCyanamid especially;
Benzophenone 9, its by BASF AG with the sold of UvinulDS49;
BP-1 0;
BP-1 1;
BP-1 2.
phenyl benzotriazole cpd:
Ethylhexysalicylate (Drometrizoletrisiloxane), its especially by RhodiaChimie with the sold of Silatrizole or by Chimex company with the title manufacture of MeroxylXL.
di-2-ethylhexylphosphine oxide (hydroxy phenyl benzotriazole) compound:
Di-2-ethylhexylphosphine oxide (benzotriazole base) tetramethyl butyl phenol; it particularly in solid form; sold with the trade name of MixximBB/100 by FairmountChemical; or to have 0.01 to 5 μm; more preferably 0.01 to 2 μm and the more especially aqueous dispersion of micronised particles of particle mean size of 0.020 to 2 μm, it has at least one and has structure C nh 2n+1o (C 6h 10o 5) xthe alkyl polyglucoside surfactant of H, wherein n is the integer of 8 to 16, and x is (C 6h 10o 5) unit average degree of polymerization and be 1.4 to 1.6; as being described in patent GB-A-2303549; sold with the trade name of TinosorbM by BASF especially; or to have 0.02 to 2 μm; more preferably 0.01 to 1.5 μm and the more especially micronised particles of particle mean size of 0.02 to 1 μm, have the polyglycereol list (C of the glycerol polymerization degree being at least 5 at least one 8-C 20) Arrcostab existence under aqueous dispersion, be such as described in the aqueous dispersion in patent application WO2009/063392.
two-resorcinol group triaizine compounds:
Two (ethylhexyl oxygen base phenol) methoxyphenyl triazine, it is sold with the trade name of TinosorbS by BASF especially.
benzoazole compounds:
2,4-two [5-(1-dimethyl propyl) benzoxazole-2-base-(4-phenyl) imino group]-6-(2-ethylhexyl) imino group-1,3,5-triazines, its especially by Sigma3V with the sold of UvasorbK2A.
In the present case and according to specific embodiments, use following organic screening agent (B):
-Ethylhexysalicylate,
Di-2-ethylhexylphosphine oxide (benzotriazole base) the tetramethyl butyl phenol of the aqueous dispersion of-micronised particles,
-bis-(ethylhexyl oxygen base phenol) methoxyphenyl triazine,
-BP-3 or oxybenzone,
2,4,6-tri-(diphenyl) triazine of-micronised form,
-and their mixture.
Organic UVA-screening agent according to the present invention is preferably with 0.01 % by weight to 30 % by weight, and preferably the content of 0.1 % by weight to 15 % by weight exists, relative to the total weight of said composition.
oil phase
At least one oil phase is comprised according to compositions of the present invention.
Compositions of the present invention comprise relative to said composition gross weight be less than 2% cyclohexasiloxane because this compound may cause the not compatible mutually problem with some oil being generally used for sunscreen formulation product.
For the present invention, term " oil phase " means the phase of at least one oil and all fat-soluble and low-polarity component and the fatty material comprised for preparing the present composition.
Term " oil " means any fatty material for liquid form under room temperature (20-25 DEG C) and atmospheric pressure (760mmHg).
Being suitable for oil of the present invention can be volatility or nonvolatile.
Be suitable for oil of the present invention can be selected from based on the oil of hydrocarbon, silicone oil and fluorocarbon oil (fluorooil) and their mixture.
Be suitable for the oil based on hydrocarbon of the present invention can be the oil based on animal hydrocarbon, the oil based on plant hydrocarbon, based on mineral hydrocarbon oil or based on synthesis hydrocarbon oil.
Be suitable for oil of the present invention can advantageously be selected from the oil based on mineral hydrocarbon, the oil based on plant hydrocarbon, based on the synthesis oil of hydrocarbon and silicone oil and their mixture.
For the present invention, term " silicone oil " means and comprises at least one silicon atom, and the oil of especially at least one Si-O group.
Term " oil based on hydrocarbon " means the oil mainly comprising hydrogen and carbon atom.
Term " fluorocarbon oil " means the oil comprising at least one fluorine atom.
Be suitable for the oil based on hydrocarbon of the present invention and optionally can also comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, such as, with the form of hydroxyl, amine, amide, ester, ether or acid groups, and particularly with the form of hydroxyl, ester, ether or acid groups.
Except lipotropy UV-screening agent (one or more), oil phase comprises at least one volatility or the nonvolatile oil based on hydrocarbon and/or a kind of volatility or nonvolatile silicone oil usually.
For the present invention, the oil that can evaporate in one hour is less than when term " volatile oil " means and contacts with skin or keratin fiber at room temperature and atmospheric pressure.Volatile oil (one or more) of the present invention is volatile cosmetic oil, and it is at room temperature liquid, and at room temperature with at particularly 0.13Pa to 40000Pa(10 -3to 300mmHg), particularly 1.3Pa to 13000Pa(0.01 is to 100mmHg) and more especially 1.3Pa to 1300Pa(0.01 to 10mmHg) atmospheric pressure under it has the vapour pressure of non-zero.
" nonvolatile oil " means and to stay at room temperature and atmospheric pressure on skin or keratin fiber at least some hours, and especially have and be less than 10 term -3the oil of vapour pressure mmHg(0.13Pa).
based on the oil of hydrocarbon
As the nonvolatile oil based on hydrocarbon that can be used according to the invention, can mention especially:
I () comes from the oil based on hydrocarbon of plant, such as triglyceride, and three esters of its normally fatty acid and glycerol, its fatty acid can have C 4to C 24the chain length of change, these chains can be saturated or undersaturated with straight chain or side chain, these oil particularly wheat germ oil, Oleum Helianthi, Oleum Vitis viniferae, Oleum sesami, Semen Maydis oil, Fructus Pruni oil (apricotoil), Oleum Ricini, shea oil (sheaoil), American Avocado Tree oil, olive oil, soybean oil, Semen pruni armeniacae oil, Petiolus Trachycarpi oil, Oleum Brassicae campestris, Oleum Gossypii semen, hazelnut oil, macadimia nut oil, Jojoba oil, Herba Medicaginis oil (alfalfaoil), poppy seed oil, squash oil, calaba oil, Ribes nigrum L. oil, Radix Oenotherae erythrosepalae oil, millet oil, large wheat oil, Quinoa oil (quinoaoil), rye-seed oil, safflower oil, candlenut oil (candlenutoil, ), passionflower oil and musk rose oil, or be also caprylic/capric triglyceride, such as sold by St é arineriesDubois those or by DynamitNobel with Miglyol810,812 and 818 those of sold,
(ii) the synthesis ether containing 10 to 40 carbon atoms;
(iii) straight chain in mineral or synthesis source or the hydrocarbon of side chain, the polyisobutylene of such as petroleum jelly, poly decene, hydrogenation, such as Parleam and squalane and their mixture;
(iv) ester synthesized, the oil of such as formula RCOOR', wherein R represents the fatty acid residue of straight chain containing 1 to 40 carbon atom or side chain, and R' represents the chain based on hydrocarbon of the especially side chain containing 1 to 40 carbon atom, condition is R+R ' is>=10, such as duck oil gland oil (purcellinoil) (the hard ester group ester (cetearyloctanoate) of cetearyl), isopropyl myristate, isopropyl palmitate, benzoic acid C 12-C 15arrcostab, such as by Witco with FinsolvTN or WitconolTN, or by EvonikGoldschmidt with the trade name product sold of TegosoftTN, benzoic acid 2-ethyl phenyl ester, such as by ISP with the commercial product of the sold of X-Tend226, isopropyl lanolate (isopropyllanolate), lauric acid hexyl ester, diisopropyl adipate, isononyl isononanoate, oleyl alcohol eruciate, Palmic acid 2-Octyl Nitrite, isostearic acid iso stearyl ester, Dermol DIPS, such as by StearinerieDubois with the product of the sold of DubDis, the caprylate of alcohol or polyhydric alcohol, decanoin or ricinoleate ester, such as propylene, hydroxylated ester, such as lactic acid iso stearyl ester or malic acid two iso stearyl ester, and pentaerythritol ester, citrate or tartrate, such as tartaric acid two (straight chain C 12-C 13alkyl) ester, such as by EnichemAugustaIndustriale with those of the sold of CosmacolETI, and tartaric acid two (straight chain C 14-C 15alkyl) ester, such as by same company with those of CosmacolETL sold, or acetas,
V () is containing side chain and/or undersaturated what contain the chain based on carbon of 12 to 26 carbon atoms is at room temperature the fatty alcohol of liquid, such as octyldodecanol, isooctadecanol, oleyl alcohol, 2-hexyldecanol, 2-butyl capryl alcohol or 2-undecylpentadecanol;
(vi) higher fatty acids, such as oleic acid, linoleic acid or linolenic acid;
(vii) carbonic ester, such as dicaprylyl carbonate (dicaprylylcarbonate), such as by Cognis company with the product of the sold of CetiolCC;
(viii) fatty acid amide, such as N-Hamposyl L isopropyl ester, such as by Ajinomoto with the trade name product sold of EldewSL205;
With their mixture.
Can be used according to the invention nonvolatile based in the oil of hydrocarbon, will more particularly preferably glycerine three ester and particularly caprylic/capric triglyceride, synthetic ester and particularly isononyl isononanoate, oleyl alcohol eruciate, benzoic acid C 12-C 15arrcostab, benzoic acid 2-ethyl phenyl ester and fatty alcohol, particularly octyldodecanol.
As volatile oil based on hydrocarbon that can be used according to the invention, the C of the oil based on hydrocarbon containing 8 to 16 carbon atoms and particularly side chain can be mentioned especially 8-C 16alkane, such as, come from the C of oil 8-C 16isoalkane (also referred to as isoparaffin), such as Fancol ID (also referred to as 2,2,4,4,6-five methylheptane), isodecane or 2-Methylpentadecane, with Isopar or Permethyl trade name sell oil, side chain C 8-C 16ester, isohexyl neopentanoate ester and their mixture.
The alkane (mixture of the different alkane distinguished by least one carbon) be described in patent application WO2007/068371 or WO2008/155059 of Cognis can also be mentioned.These alkane are available from fatty alcohol, and itself is available from Oleum Cocois or Petiolus Trachycarpi oil.N-hendecane (C can be mentioned 11) and n-tridecane (C 13) mixture, it is available from the embodiment 1 and 2 of the patent application WO2008/155059 from Cognis company.N-dodecane (C can also be mentioned 12) and the n-tetradecane (C 14), it is sold with Parafol12-97 and Parafol14-97 entry respectively by Sasol, and their mixture.
Also can use other volatile oil based on hydrocarbon, such as petroleum distillate, especially by Shell company with those of the sold of ShellSolt.According to an embodiment, volatile solvent is selected from volatile oil based on hydrocarbon containing 8 to 16 carbon atoms and their mixture.
silicone oil
Nonvolatile silicone oil can be selected from nonvolatile polydimethylsiloxane (PDMS) especially, comprise side chain (pendent) and/or at the alkyl of silicone chains end or the polydimethylsiloxane of alkoxyl, this group is respectively containing 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicone (phenyltrimethicone), phenyl dimethicones, phenyl (trimethylsiloxy) diphenyl siloxane, diphenyl dimethicone, diphenyl (methyldiphenyl base) trisiloxanes or (2-phenylethyl) trimethylsiloxysilicate ((2-phenylethyl) trimethylsiloxysilicate).
The example of the volatile silicone oils that can mention comprises volatile straight chain or cyclic silicone, especially has viscosity≤8 centistoke (8 × 10 -6m 2/ s) with especially containing those of 2 to 7 silicon atoms, these silicone optionally comprise alkyl containing 1 to 10 carbon atom or alkoxyl.As the volatile silicone oils that may be used in the present invention, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, seven methylhexyl trisiloxanes, seven Methyl Octyl trisiloxanes, hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane and ten dimethyl five siloxanes and their mixture can be mentioned especially.
The alkyltrisiloxane oil of volatile straight chain of general formula (I) can also be mentioned:
Wherein R represents the alkyl comprising 2 to 4 carbon atoms, and its one or more hydrogen atom can be substituted by fluorine atom or chlorine atom.
In the oil of general formula (I), can mention:
3-butyl-1,1,1,3,5,5,5-seven methyl three alcoxyl alkane,
3-propyl group-1,1,1,3,5,5,5-seven methyl three alcoxyl alkane, and
3-ethyl-1,1,1,3,5,5,5-seven methyl three alcoxyl alkane,
It corresponds to the oil of formula (I), and wherein R is respectively butyl, propyl group or ethyl.
fluorocarbon oil
Volatile fluorocarbon oil can also be used, such as Nonafluoromethoxybutcompositions, Decafluoropentane, Tetradecafluorohexane, R-4112 and their mixture.
Can also comprise other fatty material according to oil phase of the present invention, it is mixed in or is dissolved in oil.
Other fatty material that may reside in this oil phase can be such as:
-fatty acid, it is selected from the fatty acid comprising 8 to 30 carbon atoms, such as stearic acid, lauric acid, Palmic acid and oleic acid;
-wax, it is selected from such as following wax: lanoline, Cera Flava, Brazil wax or candelilla wax, paraffin, montan wax, microwax, mineral tallow (ceresin) or ceresine (ozokerite), or synthetic wax, such as Tissuemat E or fischer-tropsch wax;
-glue, it is selected from silicone adhesive (siliconegum) (dimethiconol);
-pasty compound, the ester of such as polymerization or non-polymeric silicone compounds, glycerol oligomers, propanoic acid eicosyl ester, fatty acid triglycercide and their derivant;
-and their mixture.
According to concrete form of the present invention, comprise can be dissolved in same mutually in total oil phase of whole lipophilic substances of described compositions represent relative to said composition gross weight 5 % by weight to 95 % by weight, and preferably 10 % by weight to 80 % by weight.
aqueous phase
At least one aqueous phase can also be comprised, especially when the organic UVA-screening agent of needs use hydrophilic according to compositions of the present invention.
This aqueous phase contain water and other optional water solublity or can be miscible with water organic solvent.
The aqueous phase be suitable in the present invention can comprise the water being such as selected from springwater, such as, from the water of LaRoche-Posay, the water from Vittel or the water from Vichy or flower water (floralwater).
Be suitable for the water solublity in the present invention or can be miscible with water solvent comprise short chain monocarbon alcohol, such as C 1-C 4monohydric alcohol, such as ethanol or isopropyl alcohol; Dihydroxylic alcohols or polyhydric alcohol, such as ethylene glycol, 1,2-PD, 1,3 butylene glycol, hexanediol, diethylene glycol, dipropylene glycol, cellosolvo, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol and sorbitol and their mixture.
According to preferred embodiment, ethanol, propylene glycol, glycerol and their mixture more particularly can be used.
According to concrete form of the present invention, comprise can be dissolved in this same mutually in total aqueous phase representative of whole hydroaropic substances of described compositions relative to 5 % by weight to 95 % by weight of said composition gross weight, and preferably 10 % by weight to 80 % by weight.
additive
A) additional UV-screening agent:
The additional UV-screening agent of hydrophilic, lipotropy, on-liquid or insoluble organic UVB-screening agent and/or one or more mineral UV-screening agent can also be selected from containing one or more according to compositions of the present invention.It will preferably be made up of at least one hydrophilic, lipotropy or insoluble organic UV-screening agent.
Term " organic UVB-screening agent " means any organic chemistry molecule of the UVB ray that can exclusively absorb in 280-320nm wave-length coverage.
Additional organic UV-screening agent is selected from Para-Aminobenzoic (PABA) compound especially; Triaizine compounds; Benzylidene camphor compound; Imidazolinium compounds; Toluenyl malonic ester compound, particularly mention in patent US5624663 those; Benzimidazole compound; Benzoazole compounds; Cover silicone and polymer, and their mixture.
As the example of additional organic UV-screening agent, can mention following represent with its INCI title those:
para-Aminobenzoic compound:
PABA,
PABA ethyl ester,
Dihydroxypropyl PABA ethyl ester,
Dimethyl PABA Octyl Nitrite, its especially by ISP with the sold of Escalol507,
PABA glyceride,
PEG-25PABA, its by BASF with the sold of UvinulP25.
benzylidene camphor compound:
Unisol S-22, its by Chimex with the title manufacture of MexorylSD,
4 methyl benzylidene camphor, its by Merck with the sold of Eusolex6300,
Polyacrylamide base methyl benzylidene camphor, its by Chimex with the title manufacture of MexorylSW.
imidazolinium compounds:
Dimethoxybenzylidenegroup group dioxoimidazolidin propanoic acid Octyl Nitrite (Ethylhexyldimethoxybenzylidenedioxoimidazolinepropionate).
toluenyl malonic ester compound:
Comprise the polysiloxane of toluenyl malonic ester functional group, such as PARSOL SLX, it is sold with the trade name of ParsolSLX by DSMNutritionalProducts, Inc especially.
4'-benzylidene malonic acid two peopentyl ester.
Mineral UV-screening agent used according to the invention is metal oxide pigment.More preferably, mineral UV-screening agent of the present invention is that average basic (elementary) granularity is less than or equal to 0.5 μm, be more preferably 0.005 to 0.5 μm, even be more preferably 0.01 to 0.2 μm, also more preferably 0.01 to 0.1 μm and the more especially metal oxide particle of 0.015 to 0.05 μm.
It can be selected from titanium oxide, zinc oxide, ferrum oxide, zirconium oxide and cerium oxide or their mixture especially.
This type of is described in patent application EP-A-0518773 especially through coating or uncoated metal oxide pigment.The commercial pigments that can mention comprises the product by SachtlebenPigments, Tayca, Merck and Degussa Company.
This metal oxide pigment can through coating or uncoated.
Pigment through coating is the surface-treated pigment having stood one or more chemistry carried out with compound, electronics, mechanochemistry and/or engineering propertiess, and this compound is such as aminoacid, Cera Flava, fatty acid, fatty alcohol, anion surfactant, lecithin, the sodium of fatty acid, potassium, zinc, ferrum or aluminum salt, (titanium or aluminum) metal alkoxide, polyethylene, silicone, protein (collagen protein and elastin laminin), alkanolamine, silicon oxide, metal-oxide or sodium hexameta phosphate.
This pigment through coating is more especially with the titanium oxide of following coating substance:
-silicon dioxide, such as, from the product Sunveil of Ikeda company,
-silicon dioxide and ferrum oxide, such as, from the product SunveilF of Ikeda company,
-silicon dioxide and aluminium oxide, such as, from product MicrotitaniumDioxideMT500SA and MicrotitaniumDioxideMT100SA of Tayca company and the Tioveil from Tioxide company,
-aluminium oxide, such as, from product TipaqueTTO-55 (B) and the TipaqueTTO-55 (A) and the UVT14/4 from SachtlebenPigments company of Ishihara company,
-aluminium oxide and aluminium stearate, such as from product MicrotitaniumDioxideMT100T, MT100TX, MT100Z and MT-01 of Tayca company, from product SolaveilCT-10W and SolaveilCT100 of Uniqema company and the product E usolexT-AVO from Merck company
-silicon dioxide, aluminium oxide and alginic acid, such as, from the product MT-100AQ of Tayca company,
-aluminium oxide and Aluminum trilaurate, such as, from the product MicrotitaniumDioxideMT100S of Tayca company,
-ferrum oxide and ferric stearate, such as, from the product MicrotitaniumDioxideMT100F of Tayca company,
-zinc oxide and zinc stearate, such as, from the product B R351 of Tayca company,
-silicon dioxide and aluminium oxide, and by silicone-treated, such as, from product MicrotitaniumDioxideMT600SAS, MicrotitaniumDioxideMT500SAS or MicrotitaniumDioxideMT100SAS of Tayca company,
-silicon dioxide, aluminium oxide and aluminium stearate, and by silicone-treated, such as, from the product STT-30-DS of TitanKogyo company,
-silicon dioxide, and by silicone-treated, such as, from the product UV-TitanX195 of SachtlebenPigments company,
-aluminium oxide, and by silicone-treated, such as, from the product TipaqueTTO-55 (S) of Ishihara company or the UVTitanM262 from SachtlebenPigments company,
-triethanolamine, such as, from the product STT-65-S of TitanKogyo department,
-stearic acid, such as, from the product TipaqueTTO-55 (C) of Ishihara company,
-sodium hexameta phosphate, such as, from the product MicrotitaniumDioxideMT150W of Tayca company,
The TiO of-use octyl trimethyl silane treatment 2, it is sold with the trade name of T805 by DegussaSilices company,
-with the TiO of polydimethylsiloxane process 2, its by Cardre company with 70250CardreUFTiO 2sI 3trade name sell,
-with the anatase/rutile TiO of polydimethylhydrogensiloxane process 2, it is sold with the trade name of MicrotitaniumDioxideUSPGradeHydrophobic by ColorTechniques company.
Can also mention and use at least one transition metal, such as ferrum, zinc or manganese, and the TiO of more especially additive Mn 2pigment.Preferably, the described pigment through doping is oil dispersion form.The oil be present in this oil dispersion is preferably selected from triglyceride, comprises the triglyceride of capric acid/sad.The oil dispersion of titan oxide particles can also comprise one or more dispersants, such as sorbitan ester, the polyoxyalkylenated fatty acid ester of such as sorbitan isostearate or glycerol, such as TRI-PPG3 myristyl ether citrate and the poly-ricinoleate ester of polyglycereol-3.Preferably, the oil dispersion of titan oxide particles comprises at least one dispersant, and it is selected from the polyoxyalkylenated fatty acid ester of glycerol.More particularly can mention the TiO with additive Mn 2the oil dispersion of granule in capric acid/Trivent OCG under TRI-PPG3 myristyl ether citrate and polyglycereol-3 gather the existence of ricinoleate ester and sorbitan isostearate, it has INCI title: titanium dioxide (with) TRI-PPG3 myristyl ether citrate (with) polyglycereol-3 ricinoleate ester (with) sorbitan isostearate, such as by Croda company with the trade name product sold of OptisolTD50.
Uncoated titanium oxide pigments is such as sold with the trade name of MicrotitaniumDioxideMT500B or MicrotitaniumDioxideMT600B by Tayca company, by Degussa company with the sold of P25, by Wackher company with the sold of TransparentTitaniumOxidePW, by MiyoshiKasei company with the sold of UFTR, by Tomen company with the sold of ITS, with by Tioxide company with the sold of TioveilAQ.
Uncoated zinc oxide pigment is such as:
-by Sunsmart company with those of the sold of Z-Cote;
-by Elementis company with those of the sold of Nanox;
-by NanophaseTechnologies company with those of the sold of NanogardWCD2025.
Through coating zinc oxide pigment such as:
-by Toshibi company with the sold of ZincOxideCS-5 those (ZnO applied with polymethyl hydrogen siloxane (polymethylhydrogenosiloxane));
-by NanophaseTechnologies company using the sold of NanogardZincOxideFN those (as at FinsolvTN, benzoic acid C 12-C 15the dispersion of 40% in Arrcostab);
-by Daito company with the sold of DaitopersionZn-30 and DaitopersionZn-50 those (dispersions in the polydimethylsiloxane of cyclopolymethyl siloxane/oxyethylation, its contain 30% or 50% with silicon dioxide and polymethyl hydrogen siloxane coating zinc oxide);
-by Daikin company with the sold of NFDUltrafineZnO those (with phosphoric acid perfluoroalkyl ester and ZnO of applying based on the copolymer of perfluor alkyl ethide, the forms with the dispersion in cyclopentasiloxane);
-by Shin-Etsu company with the sold of SPD-Z1 those (ZnO applied with the acrylate copolymer of silicone-grafting, it is scattered in ring dimethyl siloxane);
-by ISP company with the sold of EscalolZ100 those (ZnO of alumina treatment, it is scattered in ethylhexyl methoxy cinnamate/PVP-hexadecene copolymer/methyl polysilicone alkylating mixture);
-by FujiPigment company with the sold of FujiZnO-SMS-10 those (ZnO applied with silicon dioxide and polymethylsilsesquioxane (polymethylsilsesquioxane));
-by Elementis company, with those of the sold of NanoxGelTN, (concentration with 55% is scattered in benzoic acid C 12-C 15znO in Arrcostab and hydroxy stearic acid condensation polymer).
Uncoated cerium oxide pigment can be such as with those of ColloidalCeriumOxide sold by Rh ne-Poulenc company.
Uncoated iron oxide pigment is such as by Arnaud company with the sold of NanogardWCD2002 (FE45B) NanogardIronFE45BLAQ, NanogardFE45RAQ and NanogardWCD2006 (FE45R), or by Mitsubishi company with the sold of TY-220.
Iron oxide pigment through coating be such as by Arnaud company with NanogardWCD2008(FE45BFN), the sold of NanogardWCD2009 (FE45B556), NanogardFE45BL345 and NanogardFE45BL or by BASF AG with the sold of TransparentIronOxide.
Metal-oxide can also be mentioned, the particularly mixture of titanium dioxide and ceria, comprise and wait weight mixture with the titanium dioxide of silica-coating and ceria, its by Ikeda company with the sold of SunveilA, and with the titanium dioxide of aluminium oxide, silicon dioxide and silicone coated and the mixture of zinc oxide, such as by the product M261 of SachtlebenPigments Company, or with aluminium oxide, silicon dioxide and glycerol coating, such as, by the product M211 of SachtlebenPigments Company.
According to the present invention, be particularly preferred through coating or uncoated titanium oxide pigments.
According to additional UV-screening agent of the present invention preferably in compositions according to the present invention with 0.1 % by weight to 45 % by weight, and particularly 1 % by weight to 30 % by weight content exist, relative to the total weight of said composition.
B) other additive:
Can also comprise conventional cosmetic adjuncts according to compositions of the present invention, it is selected from the organic solvent be usually used in cosmetics and/or dermatological field especially, ion or non-ionic thickening agent, softening agent, wetting agent, opacifier, stabilizing agent, emollient, silicone, defoamer, spice, antiseptic, the surfactant of anion, cation, nonionic, amphion or both sexes, activating agent, filler, polymer, propellant, alkalization or acidulant or other composition any.
Can mention in organic solvent except C as defined above 1-C 4alcohol outside monohydric alcohol, and particularly short chain C 2-C 8polyhydric alcohol, such as glycerol or dihydroxylic alcohols, such as caprylyl glycol, 1,2-pentanediol, propylene glycol, butanediol, glycol and glycol ethers, such as ethylene glycol, propylene glycol, butanediol, dipropylene glycol or diethylene glycol.
As thickening agent, CVP Carbopol ETD2050 can be mentioned, such as Carbopols (carbomer) and Pemulens, such as PemulenTR1 and PemulenTR2 (acrylate/acrylic acid C 10-C 30-alkyl ester copolymer); Polyacrylamide, such as, with the cross-linked copolymer of the sold of Sepigel305 (CTFA title: polyacrylamide/C 13-14isoparaffin/lauryl polyoxyethylene (7) ether) or the Simulgel600(CTFA title of SEPPIC company: acrylamide/sodium acryloyldimethyl taurate copolymers/2-Methylpentadecane/Polysorbate (polysorbate) 80); 2-acrylamide-2-methylpro panesulfonic acid polymer and copolymer, optionally crosslinked and/or neutralization, such as poly-(2-acrylamido-2-methyl propane sulfonic acid), its by Hoechst company with HostacerinAMPS ?trade name sell (CTFA title: polypropylene acyl group dimethyltaurine ammonium) or the Simulgel800 (CTFA title: polypropylene acyl group dimethyltaurine sodium/polyoxyethylene sorbitan monoleate/sorbitanoleate) by SEPPIC Company; The copolymer of 2-acrylamide-2-methylpro panesulfonic acid and Hydroxyethyl Acrylate, such as, by SimulgelNS and SepinovEMT10 of SEPPIC Company; Cellulose derivative, such as hydroxyethyl-cellulose; Polysaccharide and particularly glue, such as xanthan gum; Water solublity or water dispersible silicone derivative, such as acrylic acid silicone, polyethers silicone and cation silicone, and their mixture.
In acidulant, the example that can mention comprises mineral acid or organic acid, such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acid, such as acetic acid, tartaric acid, citric acid or lactic acid and sulfonic acid.
In basifier, the example that can mention comprises ammonia, alkali carbonate, alkanolamine, such as monoethanolamine, diethanolamine and triethanolamine and derivant thereof, sodium hydroxide or potassium hydroxide.
Preferably, described cosmetic composition comprises one or more and is selected from alkanolamine, especially the basifier of triethanolamine and sodium hydroxide.
When direct Emulsion, the pH according to compositions of the present invention is about 3 to 12 usually, is preferably about 5 to 11 and be also more particularly 6 to 8.5.
For nursing keratin material, such as, in the activating agent of skin, lip, scalp, hair, eyelashes or fingernail, the example that can mention comprises:
-vitamin separately or as a mixture and derivant thereof or precursor;
-antioxidant;
-free radical scavenger;
-anti-fouling agent;
-tanning agent (self-tanningagents);
-anti-gfycation agent;
-tranquilizer;
-deodorizer;
-quintessence oil;
-NO-synthase inhibitor;
-promote synthesis corium or epidermal macromolecules and/or the reagent that prevents it to decompose;
-promote into the reagent of fibroblast proliferation;
The reagent of-promotion keratinocyte proliferation;
-muscle relaxant;
-freshener;
-tonicity agents (tensioningagent);
-dumb light agent (mattifyingagent);
-depigmenting agent;
-chromogen agent (propigmentingagent);
-keratolytic agent;
-decorticating agent;
-wetting agent;
-antiinflammatory;
-antimicrobial;
-slim dose;
-act on the reagent of cellular energy metabolism;
-insecticide;
-Substance P or CGRP antagonist;
-anti-alopecia agent (hair-losscounteractant);
-anti-wrinkle agent;
-antidotal agent.
Those skilled in the art, by according to effect required on skin, hair, eyelashes, eyebrow or fingernail, select described active principle (one or more).
Without the need to superfluous words, those skilled in the art by above-mentioned for attentional selection optional additional compound (one or more) and/or its amount, thus make the advantageous property that is associated inherently with compositions according to the present invention not by or the additive (one or more) that is not substantially designed affect negatively.
preparation (galenical) form
Can prepare according to the known technology of those skilled in the art according to compositions of the present invention.They can the form of specifically simple or multiple emulsion (O/W, W/O, O/W/O or W/O/W), such as cream (cream), milk (milk) or cream gel (creamgel).
They can also be anhydrous form, such as the form of oil.Term " anhydrous composition " means the water comprising and be less than 1 % by weight, or even less than 0.5 % by weight water and particularly water-free compositions, described water does not add during compositions preparation, but corresponds to the residual water that blending constituent provides.They optionally can be packed with aerosol and can be the form of mousse or spraying.
When said composition is the form of oil-in-water or water in oil emulsion, available emulsification method is blade (paddle) or impeller (impeller), rotor-stator and HPH type.
In order to obtain the stable emulsion of the polymer with low content (oil/polymer ratio >25), in concentrated middle this dispersion of preparation mutually, and then this dispersion can be diluted with remaining aqueous phase.
Also can by HPH(50 to 800bar) obtain there is the stabilising dispersions that possibility is low to moderate the drop size of 100nm.
Emulsion comprises at least one emulsifying agent usually, and it is selected from both sexes, anion, cation and nonionic emulsifier, separately or use as mixture.Emulsifying agent is selected suitably according to Emulsion (W/O or O/W) to be obtained.
The example of the W/O emulsifying surfactant that can mention comprises Arrcostab or the ether of sorbitan, glycerol, polyhydric alcohol or sugar; Silicone surfactant, such as dimethicone copolyol, the mixture of such as Cyclomethicone and dimethicone copolyol, its by DowCorning company with the sold of DC5225C, with alkyl dimethicone copolyol, such as laurylmethicone copolyol, its by DowCorning company with the sold of DowCorning5200FormulationAid; Abil EM 90, such as by Goldschmidt company with the product of the sold of AbilEM90R, with the mixture of Abil EM 90, polyglycereol (4mol) isostearate and lauric acid hexyl ester, its by Goldschmidt company with the sold of AbilWEO9.Can also add one or more coemulsifiers to it, described coemulsifier can advantageously be selected from polyhydric alcohol Arrcostab.
Non-silicone emulsifying surfactant, particularly sorbitan, glycerol, the Arrcostab of polyhydric alcohol or sugar or ether can also be mentioned.
The polyhydric alcohol Arrcostab that can mention especially comprises macrogol ester, such as PEG-30 dimerization hydroxy stearic acid ester, such as by ICI company with the product of the sold of ArlacelP135.
The glyceride that can mention and/or the example of sorbitan ester comprise isostearic acid polyglycerin ester, such as by Goldschmidt company with the product of the sold of IsolanGI34; Sorbitan isostearate, such as by ICI company with the product of the sold of Arlacel987; Sorbitan glyceryl isostearate, such as by ICI company with the product of the sold of Arlacel986, and their mixture.
For O/W Emulsion, the example of the non-ionic emulsifier surfactant that can mention comprises polyoxyalkylenated (more particularly polyoxyethylated and/or polyoxypropylene) ester of fatty acid and glycerol, the oxyalkylenated ester of fatty acid and sorbitan, polyoxyalkylenated (particularly polyoxyethylated and/or polyoxypropylene) ester of fatty acid, it is optionally combined with the ester of fatty acid and glycerol, such as PEG-100 stearate/glyceryl stearate mixture, its such as by ICI with the sold of Arlacel165, oxyalkylenated (oxyethylation and/or oxypropylation) ether of fatty alcohol, the ester of sugar, such as sucrose stearate, or the ether of fatty alcohol and sugar, particularly APG (APGs), such as decyl glucoside and lauryl glucoside, its such as by Henkel company respectively with the sold of Plantaren2000 and Plantaren1200, cetearyl glucoside, it is optionally as the mixture with cetearyl alcohol, its such as by SEPPIC company with the title of Montanov68, by Goldschmidt company with the title of TegocareCG90 and by Henkel company with the sold of EmulgadeKE3302, with Semen arachidis hypogaeae base glucoside, such as with the form of the mixture of arachidic alcohol and behenyl alcohol and Semen arachidis hypogaeae base glucoside by SEPPIC company with the sold of Montanov202.According to a specific embodiment of the present invention, alkyl polyglucoside as defined above can be the form of self-emulsifying composition with the mixture of corresponding fatty alcohol, such as, as described in file WO-A-92/06778.
When it is Emulsion, the aqueous phase of this Emulsion can comprise the dispersion of Non-ionic vesicles shape (vesicular), and it is according to known method (Bangham, StandishandWatkins, J.Mol.Biol.13,238(1965), FR2315991 and FR2416008) prepare.
Compositions according to the present invention is applied to skin, lip and hair, comprises in many kind process of scalp, especially in cosmetic treatment, in particular for protection and/or nursing skin, lip and/or hair, and/or for cosmetic skin and/or lip.
Another theme of the present invention is by compositions according to the present invention as defined above for the manufacture of the cosmetic product for the treatment of skin, lip, fingernail, hair, eyelashes, eyebrow and/or scalp, and especially the purposes of care product, sunscreen product and cosmetic product is formed.
Such as cosmetic product can be used as according to cosmetic composition of the present invention.
Another theme of the present invention is by for nurse and/or the non-therapeutic cosmetic method of keratin material of making up is formed, and the method comprises surface applied at least one to described keratin material as defined above according to compositions of the present invention.
What can be used as such as face and/or health according to cosmetic composition of the present invention has liquid to the care product of semi-liquid consistency and/or sunscreen product, such as milk or many or few smooth cream, cream gel or paste (paste).It can optionally be packed with aerosol form, and can be the form of mousse or spraying.
According to the present invention, the compositions according to the present invention of transpirable fluid dew (lotion) form is applied on skin or hair by pressurizer with fine grain form.Be known for those skilled in the art according to device of the present invention, and comprise non-aerosol pump or " nebulizer ", comprise propellant and use compressed air as the aerosol container of the aerosol pump of propellant.These devices are described in patent US4077441 and US4850517.
Usually conventional propellant, such as hydrofluorocompounds is contained, dichlorodifluoromethane, Difluoroethane, dimethyl ether, iso-butane, n-butane, propane or Arcton 11 according to the compositions that the present invention packs with aerosol form.They preferably exist, relative to the total weight of said composition with the amount of 15 % by weight to 50 % by weight.
assembly
According to another aspect, the invention still further relates to cosmetics assembly, it comprises:
I) container, it defines one or more compartment, and described container is closed by closure elements, and is be optionally unsealed; With
Ii) according to cosmetic of the present invention and/or care composition, it is positioned in described compartment (one or more).
This container can be such as the form of tank or box.
Described closure elements can be lid form, and it comprises the cap of installation, thus can relative to shell of tank by translation or move described cosmetic and/or care composition (one or more) by pivoting.
Following examples are used for illustrating the present invention, but are not restrictive in essence.In these embodiments, the amount of composition components is provided with the form of the percentage by weight relative to said composition gross weight.
Embodiment
a. the embodiment of merocyanine UV-absorbent is prepared
embodiment A 1: prepare compound (1)
By 122.23g3-[(3-methoxy-propyl) amino]-2-cyclohexene-1-ketone dimethyl sulfate or alternatively use dithyl sulfate alkylation, and at alkali with optionally in the presence of the solvent with the process of about equimolar ratio example 75.45g cyan-acetic ester.
Use following alkali/solvent combination:
Embodiment Alkali Solvent
Embodiment A 1.1 DBU(1,8-diazabicylo [5.4.0] 11-7-alkene) Dimethyl acetylamide
Embodiment A 1.2 Triethylamine Isopropyl alcohol
Embodiment A 1.3 3 methoxypropyl amine Isopropyl alcohol
Embodiment A 1.4 3 methoxypropyl amine Tert-pentyl alcohol
Embodiment A 1.5 3 methoxypropyl amine Toluene
Embodiment A 1.6 3 methoxypropyl amine Dimethyl formamide
Embodiment A 1.7 3 methoxypropyl amine Solvent-free
Embodiment A 1.8 N-morpholine Isopropyl alcohol
Such as by method, such as TLC, GC or HPLC monitor completing of alkylated reaction.
Obtain the 162.30g compound (14) of the form for brown oil.
After crystallization, the product of the form into pale yellow crystals is obtained.
Fusing point: 92.7 DEG C.
embodiment A 2: prepare compound (2)
By 148.4g3-[(3-methoxy-propyl) amino]-2-cyclohexene-1-ketone dimethyl sulfate or alternatively use dithyl sulfate alkylation, and with the process of 130.00g cyanoacetic acid 2-ethoxy ethyl ester under the existence of organic base and solvent.
Use following alkali/solvent combination:
Embodiment Alkali Solvent
Embodiment A 2.1 DBU(1,8-diazabicylo [5.4.0] 11-7-alkene) Dimethyl acetylamide
Embodiment A 2.2 Triethylamine Isopropyl alcohol
Embodiment A 2.3 3 methoxypropyl amine Isopropyl alcohol
Embodiment A 2.4 N-methylmorpholine Tert-pentyl alcohol
Embodiment A 2.5 3 methoxypropyl amine Toluene
Embodiment A 2.6 3 methoxypropyl amine Dimethyl formamide
Embodiment A 2.7 3 methoxypropyl amine Solvent-free
embodiment A 3 (scope of the invention is outer): prepare compound (2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide, it is described in unpub patent application PCT/EP2012/064195
By 101.00g3-[(3-methoxy-propyl) amino]-2-cyclohexene-1-ketone dimethyl sulfate or alternatively use dithyl sulfate alkylation, and with the acetamide process of about equimolar ratio example 86.00g2-cyano group-N-(3-methoxy-propyl) under the existence of alkali and optional solvent.
Use following alkali/solvent combination:
Embodiment Alkali Solvent
Embodiment A 3.1 DBU(1,8-diazabicylo [5.4.0] 11-7-alkene) Dimethyl acetylamide
Embodiment A 3.2 Triethylamine Isopropyl alcohol
Embodiment A 3.3 3 methoxypropyl amine Isopropyl alcohol
Embodiment A 3.4 3 methoxypropyl amine Tert-pentyl alcohol
Embodiment A 3.5 3 methoxypropyl amine Toluene
Embodiment A 3.6 3 methoxypropyl amine Dimethyl formamide
Embodiment A 3.7 3 methoxypropyl amine Solvent-free
Obtain crude product (2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-[(3-methoxy-propyl) the is amino] hexamethylene-2-alkene-1-subunit of the form for dark brown oil } acetamide.After chromatography (eluent: 99/1 toluene and methanol) on a silica gel column, obtain the product of the 81.8g of the form into pale yellow crystals.
Fusing point: 84.7-85.3 DEG C.
b.1 preparation embodiment 1 to 4
Compound 2-ethoxyethyl group (2Z)-cyano group of the present invention { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } (2) is compared with following compound:
-according to compound (2Z)-2-cyano group-N-(3-the methoxy-propyl)-2-{3-of embodiment A 3 [(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide (scope of the invention is outer)
-compound 5-N, N-diethylamino-2-benzenesulfonyl-2,4-pentadienoic acid monooctyl ester (scope of the invention is outer)
Merocyanine compound MC11 disclosed in-application WO2008/090066 (scope of the invention is outer)
Prepare following preparation 1 to 4; Building them makes the summation of the content of oil and fat-soluble UV-screening agent keep constant.The content of screening agent is regulated to make to guarantee that the UVB of phase same level covers and identical external SPF, and absorption curve identical between 290-340nm.To often kind of preparation, measure external SPF, the external UVA of room temperature after lower 24 hours and at 60 DEG C after 10 days pPDexponential sum absorbance.
Prepare following preparation 5 to 9.The content of filtering agent is constant, with comparative compound (2) under same amount with according to (2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-of embodiment A 3 [(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit acetamide (scope of the invention is outer) and apply for the performance of compound MC11 disclosed in WO2008/090066 (scope of the invention outward).For preparation 5 and 6, at room temperature a Zhou Houhe measures SPF, UVA after 45 days at 45 DEG C pPDexponential sum absorbance.Described amount is expressed as relative to said composition gross weight % by weight.
method of preparing emulsion:
By mixing parent material by mechanical agitation at 80 DEG C, prepare aqueous phase A and oil phase B.Once water solution A and oil solution B are macroscopically uniform, phase B are incorporated in phase A and prepare Emulsion, use rotor-stator homogeniser, stir 20 minutes under 4500rpm mixing speed.Then phase C is added successively under continued mixing, then phase D.Before adding phase E, this Emulsion is made finally to be cooled to room temperature.The feature of final Emulsion is the drop of 1 μm of-20 μm of size.
for assessment of the experiment in vitro scheme of obscuring effect
According to the in vitro method determination sun protection factor (SPF) described in J.Soc.Cosmet.Chem.40,127-133 (1989) by B.L.Diffey.Use and measure from the UV-1000S spectrophotometer of Labsphere company.Extract " the outer sun protection factor (SPF) of static body " value.With even and smooth deposit form with 1mg/cm 2often kind of compositions is applied to the coarse plate of PMMA by ratio.
The UV-1000S spectrophotometer from Labsphere company is used to carry out external UVA under the same conditions pPDindex measurement.Extract " UVA pPDindex (the dimmed action spectrum of lasting pigment) " value.With even and smooth deposit form with 1mg/cm 2often kind of compositions is applied to the coarse plate of PMMA by ratio.
for assessment of the experimental program of the absorption spectrum of preparation
Measure and external UVA from SPF in vitro pPDthe mAF data of the function as wavelength produced during index measurement extract the absorption spectrum of preparation.Then according to Abs=log (mAF), mAF value is changed into absorbance.
prepare the absorbance of the preparation measured after 24 hours
the absorbance of the preparation that 10 days measure afterwards at 60 DEG C
conclusion
Prepare the absorbance display of measuring under 400nm after 24 hours, for identical SPF and identical external UVA pPDindex, compared to preparation 3 and 4, preparation 1 and 2 is more ineffective.
The absorbance display of measuring under 400nm after 10 days at 60 DEG C, for identical SPF and identical external UVA pPDindex, preparation 3 is more ineffective than preparation 4 of the present invention.
at room temperature store the absorbance of the preparation 5 and 6 measured after a week
the absorbance of the preparation 5 and 6 measured afterwards for 45 days at 45 DEG C
External SPF and UVA that preparation 5 and 6 is measured pPDindex shows, and for preparation 6 according to the present invention, remains on the effect in UVB and UVA radiation in time and temperature, and declines for preparation 5 (scope of the invention is outer) effect.
In addition, the absorbance display of at room temperature measuring on preparation 5 and 6 under 400nm after a week is compared to preparation 6 according to the present invention, and preparation 5 is more ineffective significantly in long UVA.This effect is stored after 45 days more obvious at 45 DEG C.
for assessment of the experimental program of preparation color
After comparison diagram prepares thin film, the color of assessment preparation.In preparation is deposited on circle that diameter is 2.2cm, and pave to obtain reproducible sedimental thickness.Then by spectral colorimetric meter MinoltaCM2600D, in two points of thin film, colorimetric measurement is carried out.Repeat this operation twice, this causes 4 experiment values of each preparation.
Expression of results is in system (L*, has*, b*), and wherein L* represents illumination, and a* represents red-green axle (-a*=is green, and+a*=is red), and b* represents Huang-blue axle (-b* is blue, and+b* is yellow).Therefore, a* and b* states the tone (shade) of compound.
By variate L*, a* and the b* between compound (2) and compound MC11 by following formulae discovery aberration △ E*:
(△E*) 2=(△L*) 2 +(△a*) 2+(△b*) 2
△ L*=L* there is the preparation of compound MC11– L* there is the preparation of compound (2)
△ a*=a* there is the preparation of compound MC11– a* there is the preparation of compound (2)
△ b*=b* there is the preparation of compound MC11– b* there is the preparation of compound (2)
We think if △ is E*>2, and the aberration between two kinds of compounds is significant.
colorimetric measurement on preparation 6 to 9
Colorimetry result display in embodiment 6 to 9, compared to the equivalent preparation 7,8 and 9 with the compound MC11 applying for WO2008/090066, the preparation 6 with compound (2) is significantly more for yellow.
b.2 preparation embodiment 10 to 14
Compound 2-ethoxyethyl group (2Z)-cyano group of the present invention { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } (2) is compared with following compound:
-according to compound (2Z)-2-cyano group-N-(3-the methoxy-propyl)-2-{3-of embodiment A 3 [(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide (scope of the invention is outer)
-compound 5-N, N-diethylamino-2-benzenesulfonyl-2,4-pentadienoic acid monooctyl ester (scope of the invention is outer)
Merocyanine compound MC11 disclosed in-application WO2008/090066 (scope of the invention is outer)
Prepare following preparation 10 to 13; Building them makes the summation of the content of oil and fat-soluble UV-screening agent keep constant.The content of screening agent is regulated to make to guarantee that the UVB of phase same level covers and identical external SPF, and absorption curve identical between 290-340nm.To often kind of preparation, measure external SPF, the external UVA of room temperature after lower 24 hours and at 60 DEG C after 10 days pPDexponential sum absorbance.Described amount is expressed as relative to said composition gross weight % by weight.
To following preparation 13 and 14; The content of filtering agent for constant to compare under same amount according to the performance of compound of the present invention (2) with compound MC11 disclosed in application WO2008/090066 (scope of the invention is outer).Described amount is expressed as relative to said composition gross weight % by weight.
Emulsion 10 to 14 is prepared according to the identical preparation mode of embodiment 1 to 9.
External SPF and external UVA is measured under the same terms indicated before pPDexponential quantity.
for assessment of the experimental program of the absorption spectrum of preparation
Measure and external UVA from SPF in vitro pPDthe mAF data of the function as wavelength produced during index measurement extract the absorption spectrum of preparation.Then according to Abs=log (mAF), mAF value is changed into absorbance.
prepare the absorbance of the preparation measured after 24 hours
conclusion
Prepare the external UVA measured under 400nm after 24 hours pPDvalue and absorbance display, for external SPF identical in UVB scope (290-320nm) and similar absorption curve, Phenylbenzimidazolesulfonic acid/butyl methoxydibenzoylmethise combination (preparation 10) is not significantly protected than Phenylbenzimidazolesulfonic acid/butyl methoxydibenzoylmethise of the present invention/merocyanine combination (preparation 13).
Phenylbenzimidazolesulfonic acid/Phenylbenzimidazolesulfonic acid/compound 2 of the present invention combines (preparation 13) and is different from Phenylbenzimidazolesulfonic acid/Phenylbenzimidazolesulfonic acid/5-N, N-diethylamino-2-benzenesulfonyl-2, 4-pentadienoic acid monooctyl ester combination (preparation 11) and Phenylbenzimidazolesulfonic acid/Phenylbenzimidazolesulfonic acid/(2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide combination (preparation 12), difference is for comparable external SPF and UVA pPDvalue, at the significantly higher absorbance that preparation was measured after 24 hours under 400nm.
colorimetric measurement on preparation 13 and 14
The colorimetric measurement on preparation 13 and 14 is carried out under the same terms such as indicated before.
Colorimetry result display in embodiment 13 and 14, compared to the equivalent preparation 14 with the compound MC11 applying for WO2008/090066, the preparation 13 with compound (2) is significantly more for yellow.
b.3 preparation embodiment 15 to 21
Compound 2-ethoxyethyl group (2Z)-cyano group of the present invention { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } (2) is compared with following compound:
-according to compound (2Z)-2-cyano group-N-(3-the methoxy-propyl)-2-{3-of embodiment A 3 [(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide (scope of the invention is outer)
-compound 5-N, N-diethylamino-2-benzenesulfonyl-2,4-pentadienoic acid monooctyl ester (scope of the invention is outer).
Prepare following preparation 15 to 18; Building them makes the summation of the content of oil and fat-soluble UV-screening agent keep constant.The content of screening agent is regulated to make to guarantee that the UVB of phase same level covers and identical external SPF, and absorption curve identical between 290-340nm.To often kind of preparation, measure the external SPF of room temperature after lower 24 hours, external UVA pPDexponential sum absorbance.
Prepare following preparation 19 to 21; The content of filtering agent for constant with comparative compound (2) under same amount and (2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-[(3-methoxy-propyl) the is amino] hexamethylene-2-alkene-1-subunit according to embodiment A 3 acetamide (scope of the invention is outer) and apply for the performance of compound MC11 disclosed in WO2008/090066 (scope of the invention outward).For preparation 20 and 21, at room temperature a Zhou Houhe measures SPF, UVA after 45 days at 45 DEG C pPDexponential sum absorbance.Described amount is expressed as relative to said composition gross weight % by weight.
Emulsion 15 to 21 is prepared according to the identical preparation mode of embodiment 1 to 4.
External SPF and external UVA is measured under the same terms indicated before pPDexponential quantity.
for assessment of the experimental program of the absorption spectrum of preparation
Measure and external UVA from SPF in vitro pPDthe mAF data of the function as wavelength produced during index measurement extract the absorption spectrum of preparation.Then according to Abs=log (mAF), mAF value is changed into absorbance.
prepare the absorbance of the preparation 15 to 18 measured after 24 hours
conclusion
At t 24hthe absorbance of lower measurement and external UVA pPDvalue display, for absorption curve identical within the scope of UVB and identical external SPF, in the protection of UVA, the preparation 15 without merocyanine is more remarkable than preparation 18 more ineffective.
At t 24hunder the absorbance measured under 400nm also show, for absorption curve identical within the scope of UVB, identical external SPF and identical external UVA pPDindex, in the protection for long UVA, (compound 5-N is respectively containing the merocyanine outside the scope of the invention, N-diethylamino-2-benzenesulfonyl-2, 4-pentadienoic acid monooctyl ester or (2Z)-2-cyano group-N-(3-methoxy-propyl)-2-{3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } acetamide) preparation 16 and 17 significantly more ineffective than the preparation 18 comprising compound of the present invention (2Z)-cyano group { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } 2-ethoxyethyl acetate (2).
at room temperature store the absorbance of the preparation 19 and 20 measured after a week
the absorbance of the preparation 19 and 20 measured afterwards for 45 days at 45 DEG C
The external UV-A that preparation 19 and 20 is measured pPDindex shows, and for preparation 20 according to the present invention, remains on the effect in UVA radiation in time and temperature, and effect declines for preparation 19 (scope of the invention is outer).
In addition, at 45 DEG C, the absorbance display preparation 19 measured on preparation 19 and 20 under 400nm after 45 days is stored significantly more ineffective in long UVA than preparation 20 according to the present invention.
colorimetric measurement on preparation 20 and 21
The colorimetric measurement on preparation 20 and 21 is carried out under the same terms such as indicated before.
Colorimetry result display in embodiment 20 and 21, compared to the equivalent preparation 21 with the compound MC11 applying for WO2008/090066, the preparation 20 with compound (2) is significantly more for yellow.

Claims (23)

1. cosmetics or dermatological compositions, in physiologically acceptable carrier, it comprises:
A) at least one oil phase, and
B) the merocyanine compound of formula (1) that defines hereinafter of at least one, and
C) the organic UVB-screening agent of at least one, it is selected from:
I) the organic UVB-screening agent of liquid lipophilic
Ii) the organic UVB-screening agent of hydrophilic
Iii) triazine UVB-screening agent and
Iv) their mixture; With
D) the organic UVA-screening agent of at least one except described merocyanine compound;
When described UVB-screening agent is liquid and is lipotropy, described compositions comprises the cyclohexasiloxane being less than 2 % by weight, relative to the total weight of said composition.
2. compositions according to claim 1, one or more merocyanine compounds of wherein said formula (1) are selected from those wherein:
R is C 1-C 22alkyl, it can be interrupted by one or more O.
3. according to the compositions of claims 1 or 2, one or more merocyanine compounds of wherein said formula (1) are selected from following compound, and itself E/E-or E/Z-geometric isomer form:
4. compositions according to claim 3, one or more merocyanine compounds of wherein said formula (1) are selected from following compound, and itself E/E-or E/Z-geometric isomer form:
5. compositions according to claim 4, wherein said merocyanine compound is (2Z)-cyano group { 3-[(3-methoxy-propyl) is amino] hexamethylene-2-alkene-1-subunit } 2-ethoxyethyl acetate (2), and it has following structure in its E/Z geometric configuration:
And/or in its E/E geometric configuration, there is following structure:
6., according to the compositions of any one of claim 1-5, wherein the organic UVB-screening agent of one or more liquid is selected from:
-liquid lipophilic β, β-diphenylacrylate ester compounds
-liquid lipophilic salicylate compounds
-liquid lipophilic cinnamate compound
-and their mixture.
7. compositions according to claim 6, wherein the organic UVB-screening agent of one or more liquid is selected from:
-octocrylene,
-homosalate,
-ethylhexyl salicylate,
-ethylhexyl methoxy cinnamate, and their mixture.
8. compositions according to claim 7, wherein the organic UVB-screening agent of one or more liquid is selected from:
-octocrylene,
-ethylhexyl salicylate, and their mixture, and be even more particularly octocrylene.
9., according to the compositions of any one of claim 1-5, wherein one or more hydrophilic UVB-screening agent is selected from:
-hydrophilic cinnamon derivative, such as ferulic acid;
-hydrophilic benzylidene camphor compound;
-hydrophilic phenylbenzimidazol compound;
-hydrophilic Para-Aminobenzoic (PABA) compound;
-hydrophilic salicylic acid compound;
-their mixture.
10. compositions according to claim 9, wherein one or more hydrophilic UVB-screening agent is selected from hydrophilic phenylbenzimidazol compound, and is more particularly compound Phenylbenzimidazolesulfonic acid.
11. according to the compositions of any one of claim 1-5, and wherein one or more triazine UVB-screening agent are selected from the 1,3,5-triazines derivant of following formula (I)
Wherein group A 1, A 2and A 3, it can be identical or different, is selected from the group of formula (II):
Wherein:
-X a, it can be identical or different, represents oxygen or-NH-group;
-R a, it can be identical or different, is selected from straight chain or side chain C 1-C 18alkyl group; C 5-C 12group of naphthene base, it is optionally by one or more C 1-C 4alkyl group replaces; The polyoxyethylated group based on hydrocarbon, it comprises 1-6 ethylene oxide unit, and wherein terminal OH groups is methylated; The group of following formula (III), (IV) or (V):
Wherein:
-R 1for hydrogen or methyl group;
-R 2for C 1-C 9alkyl group;
-q is the integer of 0-3;
-r is the integer of 1-10;
-A' is C 4-C 8alkyl group or C 5-C 8group of naphthene base;
-B' is selected from: straight chain or side chain C 1-C 8alkyl group; C 5-C 8group of naphthene base; Optionally by one or more C 1-C 4the aromatic yl group that alkyl group replaces;
Understand, work as A 1, A 2and A 3identical and X awhen representing oxygen atom, then R arepresent side chain C 6-C 18alkyl group.
12. compositionss according to claim 11, the triazine UVB-screening agent of wherein said formula (I) is selected from following compound:
-corresponding to the 2-[(p-(tert-butyl amide groups) anilino-]-4,6-of following formula two [(p-(2 '-ethylhexyl-1 '-oxygen base carbonyl) anilino-]-1,3,5-triazines:
Wherein R''' represents 2-ethylhexyl group, and R'' represents tert-butyl group;
-corresponding to 2,4,6-tri-[p-(2'-ethylhexyl-1'-oxygen base carbonyl) anilino-]-1,3,5-triazines of following formula:
Wherein R''' represents 2-ethylhexyl group,
-and their mixture.
13. according to the compositions of any one of claim 1-5, and wherein one or more triazine UVB-screening agent are selected from the silicone triazine of following formula (VI), or its tautomeric form:
Wherein:
-R 1, it can be identical or different, represents straight chain or side chain C 1-C 30hydrocarbyl group, it is optionally halogenated or undersaturated, C 6-C 12aromatic yl group, C 1-C 10alkoxy base, oh group or trimethylsiloxy group;
-a=1 is to 3; Except formula A (Si) (R) a(O) (3-a)/2unit outside,
-group (D) represents the sym-triazine compound of following formula (VII):
Wherein:
-X represents-O-or-NR 10-, R 10represent hydrogen or C 1-C 5alkyl group,
-R 8represent optionally undersaturated straight chain or side chain C 1-C 30hydrocarbyl group, and it can comprise silicon atom, C 5-C 20group of naphthene base, it is optionally by 1-3 straight chain or side chain C 1-C 4alkyl group replaces, group-(CH 2cHR 10-O) mr 11or group-CH 2-CH (OH)-CH 2-O-R 12,
-R 9, it can be identical or different, represents oh group, straight chain or side chain C 1-C 8alkyl group or C 1-C 8alkoxy base, the R of two vicinities on identical aromatic ring 2group can form alkylenedioxy group group together, and wherein alkylidene group contains 1 or 2 carbon atom,
-R 10represent hydrogen or methyl; Group (C=O) XR 8relative to amino group can at ortho position, a position or para-position,
-R 11represent hydrogen or C 1-C 8alkyl group,
-R 12represent hydrogen or C 4-C 8alkyl group,
-m is the integer of 2-20,
-n=0 to 2,
-A is for being selected from methylene or corresponding to following formula (VIII), (IX), (X) or (XI) one of them divalent group of group:
Wherein:
-Z is the C of saturated or unsaturated, straight chain or side chain 1-C 10alkylidene divalent group, it is optionally replaced by oh group or oxygen atom and optionally comprises amino group;
-W represents hydrogen atom, oh group or straight chain or side chain, saturated or undersaturated C 1-C 8hydrocarbyl group; The organosilicone compounds of described formula (VI) can also contained (R 1) b-(Si) (O) (4-b)/2unit, wherein R 1have and the identical meanings in formula (VI), b=1,2 or 3
14. compositionss according to claim 13, the triaizine compounds of its Chinese style (VI) is represented by following formula (VIa), (VIb) or (VIc):
(VIc)(D)-Si(R 14) 3
Wherein:
-(D) corresponding to formula as defined in claim 8 (VII),
-R 13, it can be identical or different, is selected from straight chain or side chain C 1-C 20alkyl, phenyl, 3,3,3-trifluoro propyls and trimethylsiloxy group or oh group,
-R 14, it can be identical or different, is selected from straight chain or side chain C 1-C 20alkyl and alkenyl group, oh group or phenyl group,
-(B), it can be identical or different, is selected from R 13group and (D) group,
-r is the integer of the 0-200 comprising end points,
-s is the integer of 0-50, and if s=0, then at least one in two (B) symbols represents (D),
-u is the integer of 1-10,
-t is the integer of 0-10, understanding be that t+u is equal to, or greater than 3, and their tautomeric form.
15. compositionss according to claim 14, the triaizine compounds of wherein said formula (VI) is structure (VI 2) two (the n-butyl ester of 4'-bis-base amino benzoic Acid)-6-{ [1,3,3,3-tetramethyl-1-[(trimethyl silyl) oxygen base] disiloxane base] propyl group-3-bases of compound 2,4-amino-sym-triazine:
16. according to the compositions of any one of claim 1-15, and wherein one or more organic UVA-screening agent are selected from:
Organic UVA-screening agent of-type (A), it exclusively can absorb the UV ray of 320-400nm,
Organic UVA-screening agent of-type (B), it can the UV ray of simultaneously stability 280-320nm and 320-400nm,
-and their mixture.
17. compositionss according to claim 16, organic UVA-screening agent of wherein said type (A) is selected from dibenzoylmethane compounds; The amino hydroxybenzophenone compound replaced; O-amino benzoyl acid compound; Benzylidene camphor compound; 4,4-diaryl adiene cpd; Two-benzoxazolyl stilbenes; With their mixture.
18. compositionss according to claim 17, organic UVA-screening agent of wherein said type (A) is selected from following compound:
-butyl methoxydibenzoylmethise;
-2-(4-diethylamino-2-hydroxy benzoyl) the n-own ester of benzoic acid;
-Terephthalidene Dicamphor Sulfonic Acid, and their mixture.
19. compositionss according to claim 16, organic UVA-screening agent of wherein said type (B) is selected from benzophenone cpd; Phenyl benzotriazole cpd; Di-2-ethylhexylphosphine oxide (hydroxy phenyl benzotriazole) compound; Two-resorcinol group triaizine compounds; Benzoazole compounds; By the triazine of the symmetry that naphthyl or polyphenylene replace; With their mixture.
20. compositionss according to claim 19, organic UVA-screening agent of wherein said type (B) is selected from following compound:
-Ethylhexysalicylate,
Di-2-ethylhexylphosphine oxide (benzotriazole base) the tetramethyl butyl phenol of the aqueous dispersion of-micronised particles,
-bis-(ethylhexyl oxygen base phenol) methoxyphenyl triazine,
-BP-3,
2,4,6-tri-(diphenyl) triazine of-micronised form,
-and their mixture.
21. for nursing and/or the non-therapeutic cosmetic method of keratin material of making up, and it comprises surface applied at least one to described keratin material as the compositions defined in front any one of claim.
22. is dimmed and/or improve the non-therapeutic cosmetic method of colour of skin color and/or colour of skin uniformity for limiting skin, and it comprises surface applied at least one to described skin as the compositions defined in front any one of claim.
23. for preventing and/or the non-therapeutic cosmetic method of processing angle protein material aging sign, and it comprises surface applied at least one to described keratin material as the compositions defined in front any one of claim.
CN201480017062.1A 2013-01-21 2014-01-20 Include the cosmetics or dermatological compositions of merocyanine, organic UVB- smoke agents for shielding and additional organic UVA- smoke agents for shielding Active CN105431130B (en)

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FR1350492 2013-01-21
FR1350493 2013-01-21
FR1350493A FR3001140B1 (en) 2013-01-21 2013-01-21 COSMETIC OR DERMATOLOGICAL COMPOSITION COMPRISING A MEROCYANINE, A HYDROPHILIC ORGANIC UVB FILTER AND AN ADDITIONAL ORGANIC UVA FILTER
FR1350492A FR3001139B1 (en) 2013-01-21 2013-01-21 COSMETIC OR DERMATOLOGICAL COMPOSITION COMPRISING A MEROCYANINE, A LIQUID LIPOPHILIC ORGANIC UVB FILTER AND AN ADDITIONAL ORGANIC UVA FILTER
FR1350494A FR3001141B1 (en) 2013-01-21 2013-01-21 COSMETIC OR DERMATOLOGICAL COMPOSITION COMPRISING A MEROCYANINE, A TRIAZINE UVB FILTER AND AN ADDITIONAL ORGANIC UVA FILTER
FR1350494 2013-01-21
PCT/EP2014/051032 WO2014111574A1 (en) 2013-01-21 2014-01-20 Cosmetic or dermatological composition comprising a merocyanine, an organic uvb-screening agent and an additional organic uva-screening agent

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CN112424162A (en) * 2018-07-12 2021-02-26 巴斯夫欧洲公司 Method for crystallizing merocyanine
CN114450375A (en) * 2019-10-11 2022-05-06 住友化学株式会社 Adhesive composition

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